V-59

The secondary purpose of this campaign was to investigate the flow characteristics of
uranium during extrusion by extruding a billet composed of a series of one-inch-thick

discs welded together,

Experimental Work

1. General

Procedures again corresponded generally to those of previous campaigns at Dow.
Constant extrusion conditions are listed in Table VI and extrusion conditions for

individual rods are listed in Table VII.



I-25

For such a reactor system the free volume of the reactor becomes

RO h : :
wv - _ - §,h - ; (Sy Sp + VSS sf ),
3
where
S_ = cross-section of shell, sq fe,

SS - §)-S, “ cross-section of mandrelat bottom, sq ft,

Si = S_-S_ = cross-section of mand:elat top, sq ft, and

other. symbols are as defined above. Substitution of equations 6) and 7), which have been altered
slightly for a fluidizing velocity of 1.75 ft/sec instead of 1.8 ft/sec, and equations 8) and 9) in

equation 11) yields

0.0520 R
Se [»7 +. SPF Sy +458 = 10°Q - VSq-Sp) Gp 4.58% 10")

= 7.16x 107°.Q,

For appropriate values of S,, Q and R, trial and error solution of equation. 12) provided che data
of Table Il. For Cases HI-E and I-F,which represent use of more than one mandrel,che sum of

the individual mandrel cross-sectional areas is S3 or St.

Case III-A was calculated to determine the feasibility of using an existing reactor shell and was

rejected because of che large fiuidizing gas rate required.
Case III-B was rejected because of excessive height.

Case III-C was less favorable than Case III-D because of a narrower annular space, which might

result in less stable fluidization

Cases IlI-D, -E, and -F were of interese, but were discarded in favor of Case III-G because the

latter reactor has a larger bottom annular space, a lower pressure drop, and a shorter height
Case III-H was discarded because of the low production cate.
The chosen design, then, is Case III-G.

It was mentioned above that the taper of the cone should theoretically be curved. As a compromise
between the fabrication expense of a theoretical taper, and the desire for the best approximation

to it, a mandrel with several straight capers will be fabricated. The mandrel dimensions are
presented in Table IV. The diameters were computed with equation 13), which was derived from

the assumption that cross-sectional area multiplied by pressure equals a constant



Daniel W. McKeel, Jr., MD

SEC-00079 co-petitioner

Southern Illinois Nuclear Workers (SINEW)
Phone: 573-323-8897

Fax: 573-323-0043

E-mail: danmckeel2@aol.com

US Mail: P.O. Box 15, Van Buren, MO 63965-0015


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v-79

All rods except No. 9 were separated from their butts when the punching operation was
used. No extrusion defect was revealed on cropping the back end of any of the rods
except No. 1. The billet from which this rod was extruded was partially melted duting
heating, so an extrusion defect could be expected in this case. Cropping of a
considerable amount of metal from the back end of Rod 6 was necessary, but this was
not co remove extrusion defect and the metal removed was not included in the cropping
loss. Apparently the graphite crushed during punching and was forced into the back end,
expanding the periphery, and causing deep longitudinal cracks in the last 12 inches of

the rod.

The grooved follower blocks used with Billets 9 and 10 did not crush sufficiently to free
the rods from their butts. However, a flat impression about seven inches in diameter

was made in the back side of the butts.

Billet 7 was completely upset and filled the container except for about one inch of its

front corner.

Discussion of Results

The low yields were due to heavy burt losses, which are attributable to the relatively
long transfer times and difficulty in calibrating the temperature recotder-controllers.
The absence of extrusion defect on cropping a small amount from the back ends of the

rods indicates that the 10° angle on the follower block contour is near the optimum.

The punch diameter apparently has no effect on the effectiveness of the punching
operation. In fact, it is not necessary to have the front of the punch pass into the die
orifice, if there is sufficient thickness of graphite behind the butt. Billet 9 revealed
thac a minimum thickness of two inches of graphite at the center is required. Solid
follower blocks worked equally as well as plugged. Alignment of the punch is an
important requisite to success of the punching operation, to prevent punch breakage and

die damage.

Although the rods extruded with grooved follower blocks were not separated from their
butts as expected, the face that the center portion of the butt was indented indicates
that redesign of this type of follower block along the same lines would probably result

in an acceptable process.



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AOI

billet

black oxide

brown oxide

derby

dingot

DMFL

‘
a

ESU

green salt
1& E slug
ingot

MFL

NOK

OK-liquor

orange oxide

P-D

preignition time

Glossary of Specialized Terms

ammonium oxalate insoluble

a bar of forged dingot uranium suitable for subsequent rolling
U,0,

uo,

the uranium metal product of the nominal 300-, 100-, and 500-Ib
reduction bombs which is subsequently recast

(direct ingot) che uranium metal product of 1400- and 3300-lb
reduction bombs. This metal not recast.

dingot magnesium fluoride liner

distribution coefficient (organic to aqueous)
easily soluble uranium

UF,

(hollow) internally and externally cooled slug
recast uranium metal

magnesium fluoride liner

a uranyl nitrate solution obtained by stripping uranyl nitrate from
tributyl phosphate-hexane solvent with water

the uranyl nitrate liquor of highest purity used as a feed to the
denitration pots

uO,
pumper-decantet
time interval between placing bomb in hot furnace and initiation

of reduction reaction

.(cquzinued on next page)

103



e

V-39

for extrusion of dingot size billets ar Weldon Spring is nearing completion. Two paralled
programs, differing in scale, to develop techniques for the operation of this press have been

in progress and are now considered essentially complete.

A relatively small-scale program, utilizing 6'{,-inch-diameter billets machined from forged
dingot stock, has been conducted at the Adrian, Mich., plant of the Bridgeport Brass Co. as
a joint endeavor of MCW and BBC. This program was designed for initial investigations of
various factors for feasibility and scope. The ninth campaign of this program, conducted on

February 26 and 27, 1958, is reported below.

A program on a scale comparable to that contemplated for Weldon Spring has been performed
under the direct control of MCW at the Madison, Ill.)-plant of the Dow Chemical Co. Most of
the work in this program consisted of scaling up factors originally investigated at Adrian. The
billets used in this program were 16% inches in diameter and were machined from full size as-
cast dingots. Reported below are the seventh, eighth, and ninth campaigns of this program,
conducted respectively on April 17 and 18, May 9, and June 7, 1958.

Most of the earlier work had been concentrated on improvement of yields. Extrusion with a
minimum of lubrication was found to give improved rod surface quality? and convex billet

back ends gave indications of reducing rod back-end losses attributable to “extrusion defect.”
However, the realization that graphite follower blocks would not crush sufficiently to free the
rods from their butts, under the pressure available on the Weldon Spring press, has revealed a
problem of considerable importance. Work at Adrian has continued toward the objective of
improving yields, while work at Dow has been directed toward developing methods for freeing
rods from their butts, as well as improving yields. For reasons involving both health problems
and press configuration, neither a shear nor a saw has been incorporated in the design of the
Weldon Spring press, aad conventional methods of separating rods and butts are thus not

available.

UI. ‘Ninth Campaign at BBC, Adrian

A. Purpose

The primary purpose of this campaign was to evaluate the effect on yield of various depths
of follower block contour between the two-in. and 4%-in. depths employed in the eighth
campaign.* Also, an evaluation of the service life of a chrome carbide insert die was

continued.

Dean, T. N., Ellerman, W. E., Schaffer, H. J., Process Development Quarterly Report, Pazt Il, Mallinckrodt Chemical
Works, MCW-1613 (May 1, 1958), p 81-89

* Dean, T. N., ef al.. MCW-14613, p 89-96

* Dean, T. N., ef al., MCW-1613, p 62-72



V-64

approximately 400 tons had been reached. The mandrel was held very tightly in the

butt after each punching experiment.

The full capacity of the press was used on Billet 11, since no study of yield was
involved. The graphite follower block was crushed and the rod was freed from its

burt without shearing

A shear-type chrome carbide insert die was used for all billets except those used in

the punching experiments; a steel die was used for these.

4. Rod Evaluation

Yields for all of the rods except Rods 9 and 11 were determined in the same manner
as described for the seventh campaign. Rods 9 and 11 were cut into one-inch-thick

transverse slices and these slices will be radiographed.

Experimental Results

Yields for the individual rods are listed in Table VIII. None of the copper or cast iron
follower blocks extruded because they did not have sufficient flowability at the cemper-
atures at which they were used. Also,since the temperatures of these follower blocks
were considerably below those of the billets, the back ‘ends of the billets were chilled
and heavy butt losses were sustained. The uranium follower block was extruded, but
did not separate from the rod. It was necessary to shear all of the rods except those

which were punched and Rod 11, which was extruded with the capacity of the press.



IV-35

Discussion of Results

The results in Table III indicate a final uranium content in fluorinated MFL (Runs 1-6) of ap-

proximately 0.15-0.20% U. The results for the fluorinated RMF dust (Runs 7 and 8) are obscured
by the formation of UO,F,; however, the values for free uranium are consistent with those for the
fluorinated MFL. These results also indicate that the metallic uranium is essentially completely

fluorinated, the major portion of the uranium remaining in the slag being the oxides.

The magnesium and magnesium oxide analyses in Tables II and III indicate that these constit-
uents are unreactive at these operating conditions. There are some anomalies in the data on

magnesium but they are felt to be a result of sampling difficulties.

The screen analyses of the slag feed and the fluorinated slag do not indicate a significant

change in the particie size distribution.

The results shown in Table IV indicate that there is no correlation between slag feed rate and
uranium content of the fluorinated MFL. These results also indicate that successful conversion
tates may be obtained at fluorine excesses as low as 1.4 times theory based on the total uranium

content of the feed.

The results shown in Table V do not indicate a correlation between the particle size of the
fluorinated slag and its uranium content. The results for Run 5 are somewhat obscured by the

formation of UO,F,; however, the U° results seem to. substantiate the Run 4 results.
The retention time for Run 6 is one hour, based on the feed rate and the measured holdup.

The severe deterioration of the reactor screw is probably caused by the cyclical formation of a
fluoride film on the metal and removal of this film by abrasion. If the shafe broke during an early
run, the difference in the deterioration of the two 5-foot sections may be attributed to this fact.
It is also conceivable that the two 5-foot sections were fabricated from different metal heats.

It is possible that by supporting both ends of the screw the deterioration may be considerably

reduced at the discharge end.

Although there was little visable damage to the reactor tube, the corrosion rate, based on the
measurements in Table VILis quite high. The results in this table also indicate that the cor-

rosion rate at the idle end may be substantially seduced by supporting the screw at this end.



Vi.

V-67

Ninth Campaign at Dow

A.

Purpose
The purposes of this campaign were to investigate further methods of freeing rods from
their butts, to investigate the flow of uranium in upsetting prior to extrusion, and to
investigate the effect of billet taper, such as is contemplated for Weldon Spring, on
heating and extrusion characteristics. Punching and the use of graphite follower blocks
weakened by having grooves machined in them,to promote controlled crushability, were
the methods under consideration for freeing rods from their burrs.
Experimental Work
1. General
Procedures were in general the same as for previous Dow campaigns. Extrusion
conditions are listed in Tables IX and X.
Table IX
Constant Extrusion Conditions - Ninth Gamma Extrusion Campaign
at Dow, Madison, Illinois
Billet Temperature 1850°F
Hot Follower Block Oven Temperature 1850°F
Warm Follower Block Oven Temperature 890°F
Tool Oven Temperature 890°F
Container Temperature 880°F
Follower Block Material CS 312 Graphice
Die Material All. Lud. Grade CA815
Chrome Carbide Insert
(in AISI H-13 Case, 50-54 R,)
Die Design Flow Type, %-in-inlet radius,

Yin. and '{,-in. offset relief



UNGLASSIFi£p

104

caffinace

RMF

rod
shotgun
slag
slug

soda-salt

UNH

U-Mag

701-metal

C-701

Glossary (continued)
the aqueous residue remaining after tributyl phosphate extraction of a
uranium concentrate previously digested with HNO,

reject magnesium fluoride

cylindrical length of uranium produced by rolling or extruding uranium
billets or ingots

a per cent increase of neutron absorption cross-section due to impurities
in the product; pure U,O, has a shotgun of zero

magnesium fluoride, containing small quantities of uranium and
magnesium formed in the thermite bomb reaction

rods of uranium machined to specific diameter and lengths. Slugs, when
canned, are used as fuel elements.

sodium diuranate; usually applied to raw materials of that composition
uranyl nitrate hexahydrate

a product of the physical separations plant consisting of a mixture of
fine metal particles, uranium oxides, and magnesium fluorides, screened
to -10 mesh and assaying 70-75% uranium

an intermediate product of the physical separations plant consisting of
the +10 mesh oversize from the screening of ground RMF. It is further
separated to 701-metal and C-701. .

the metal concentrate product of the physical separations plant
consisting of uranium metal particles ranging in size from +10 mesh to
1/2 inch and assaying 95% uranium

the rejece product of the physical separations plant consisting chiefly
of finely ground magnesium fluoride

~smseaen A ich de  ore:

ee


«

C. Experiment

4. Evaluation

Evaluation of the rods was performed in the same manner as the rods from previous

Adrian campaigns.

1 Results

Yields for individual rods are listed in Table Il. The relationship of the yields to the
cylindrical-conical volume ratios of the billets heated in open-end cans is shown in

Figure 2.

The “reverse pipe” type of defect encountered in rods from the eighth gamma campaign
at Adrian* was again the cause of high back-end losses and low yields. Surfaces of all

of the rods were of acceptable quality for rolling.

The chrome carbide die used, while exhibiting myriad fine cracks, was still usable after
this campaign. The die had been used for extrusion of a total of 47 rods at the completion

of this campaign.
Discussion of Results

The yields obtained were, in general, much lower than desired and would not be acceptable

for a manufacturing process

A striking difference was noted between the yields for billets heared in open-end cans and
those heated in solid-end cans. All of the former were above 75%, while all but two of
the latter were below 75%. For this reason only yields for billets heated in open-end cans
are included in Figure 2. The average of the yields for billets heated in open-end cans
was 79.6%, while for chose heated in solid-end cans it was 73.8%. Cropping losses were
primarily responsible for the difference ia avecage yields, being 14.9% and 20.8%,
respectively. There was no noticable difference in the pattern of the back-end defect
(ceverse pipe) for rods extruded from billets heated in either type of can, excepr that it
extended further into those rods extruded from billets heated in solid-end cans. Since all
of the solid-end cans ruptured during heacing in the muffle furnace, there was undoubtedly
a greater amount of oxide on the surface of the billets heated in these cans during
extrusion. This oxide layer may have changed the flow pagrern of the metal during
extrusion, because of a change in friction between the billet and container liner, resulting
in @ greater chan normal extrusion defect, or the oxide may have been enfolded during

extrusion to form additional extrusion defect.

© Dean, T. N., ef al., MCW-1613, p 70



VI-87

Table II (continued)

Time Average
Syntron Duration Feed Rate
Setting min lb/hr
80 6 35.3
80 6 45.7
80 6 33.2
80 6 33.2
80 6 42.6
85 3 76.3
85 3 73.6
85 3 78.9
85 3 82.7
85 3 82.1

a . ,
The runs were made consecutively in the order shown without

shutdown,

Table IIL

Particle Diameter of Micronized UO,
from Run No. 14

Clock Mean Particle Diameter
Tine __migron

1000 0.68

1300 71

1400 83

1600 96





eo

Date of Issue: August 1, 1958 Report Number: MCW-1416
Subject Category: Technology - Feed Materials
(M-3679, 22nd Ed.)

PROCESS DEVELOPMENT QUARTERLY REPORT
PART Il - PILOT PLANT WORK

edited by John Nelson

The work reported herein was done under the

general supervision of the following

‘ isssilication
F

b B co eeeeeeeee TE, ditee- 2-60

N. E. Berry

Technical Director

A. E. Ruehle

Assistant Technical Director

R. M. Edwards J. A. Fellows
Manager, Process Development Manager, Metallurgical Development
C. W. Kuhlman, Jr. J. U. Shepardson
Manager, Laboratory Development Manager, Analytical Laboratory
E. L. Miller

Plant Manager, Operations Division

J. H. Yeager
Manager, Production Technology

This is a progress report on current work and is issued as promptly as possible at che

end of the quarter. Asa result, it is subject to inaccuracies.

PATA

Ud in the Atomic Energy Act of 1954. Its transmittal

to any unauthorized person is prohibited.

Mallinckrodt Chemical Works

St. Louis, Missouri

UNCLASSIFIED aa:



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sane / bitter
» wy

Ni y

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\

Follower Blocks:
Plugged, Wor (Fig. tie)
Plugged, Warm (Fig. 11b)
Hollow, Warm (Fig. ila)

=

Lo SSS
“f aR 1
Follower Blocks:
Soltd, Hoe (Ffg. tg)
C___ solid, Warm (Fly. 11)
Hollow, Warm (Fig. tla)

—

Billet {
\ y
ASS h
SSS -
NI

Follower Blocks:
Me)

lugged, Hot (Fig
l lollow, Warm (Fig. La)

Billecy

FIGURE 17?

Follower Blocks:
Solid, Hot (Fig. lle)
Solid, Warm (Fig.

9 And &

Billets 5

Follower Biocks:
L. ceooved, Hot (Fig.
Solid, Warm (Fig.
ET Hot low, Warm (Fig

Bille And 10

ARRANGEMENT OP FOLLOWER BLOCKS FOR VARIOUS BILLETS,
NINTH CAMPAIGN AT DOW

V-73

td)
Hollow, Warm (Pig. lla)

ty)
10)
ila)


VI-82

Feed

a Horper
Korver

Nozzle

Product
Outlet ———»

Grinding Top

Air Inlet rigte Venturi
Tube

Bottom__/

Plate

PIGURE 1
MICRONIZER DETAILS



Miller, Diane M. (CDC/NIOSH/EID)

— ——
From: DanMcKeel2@aol.com

Sent: Monday, July 12, 2010 7:18 AM

To: NIOSH Docket Office (CDC); Hinnefeld, Stuart L. (CDC/NIOSH/OD); melius@nysliuna.org
Ce: danmckeel2@aol.com; Wade, Lewis (CDC/NIOSH/OD) (CTR); Katz, Ted (CDC/NIOSH/OD)
Subject: New scientific data on Dow Madison IL SEC-00079

Attachments: MCW-1416_1217030.pdf

Docket 113 (Dow Madison)

Docket 194 (NIOSH 10 Year Review)

Stuart Hinnefeld, Acting Director, DCAS/NIOSH

Dr. James Melius, chair, ABRWH and SEC Issues WG
cc: Dr. Lewis Wade, former ABRWH DFO

cc: Ted Katz, present ABRWH DFO

July 12, 2010
Docket Office, Mr. Hinnefeld and Dr. Melius,

| want to bring to your attention the existence, source and content of new scientific information related to Dow SEC-00079,
that is the attached PDF file from DOE-OSTI that is AEC/MCW declassified technical report MCW-1416. The article
"GAMMA EXTRUSION OF ‘DINGOT' METAL" by T. N. Dean and W. E. Ellerman on pages 37-80 is relevant to Dow SEC-
00079. To my knowledge, this publication is not mentioned in reference citations in Dow technical documents that
NIOSH/ORAU has prepared to date. Please post this message to both the Dow DOCKET #113 and to Docket 194 if
possible (the formal comment period closed 6/5/10).

Report MCW-1416 includes a section that more accurately characterizes the AEC contract work between Mallinckrodt
Chemical Works Uranium Division ("MCW") and the Dow Chemical site in Madison, illinois ("Dow"). Dow has been
awarded 83.14 SEC-79 (1957-60). Extension of this SEC to cover the 1961-2007 residual contamination period for
uranium and thorium is being considered by the ABRWH ("Board") and by the SEC Issues work group that are both
headed by Dr. Melius.

The new information in MCW-1416 concerns the number of experimental R&D uranium gamma phase extrusion
campaigns that AEC-MCW contracted to be performed at the Dow, IL facility. The NIOSH-prepared Dow SEC-79
evaluation report and Appendix C to Battelle TBD-6000 both indicate there were only two (2) known gamma phase R&D
uranium extrusion campaigns at Dow. The new information being introduced, AEC report MCW-1416 (PDF attached),
indicates there were actually nine (9) gamma phase uranium extrusion campaigns that were carried out at Dow. The
relevant section on the Dow gamma phase extrusion campaigns is pages 37 through 80. Pages V37-V38 provide an
overview of the 7th, 8th and 9th Dow R&D gamma phase extrusion campaigns that are described separately in MCW-
4416. The importance of this new information is (a) to increase the uranium source term size at Dow significantly (from 2
to 9 campaigns), and (b) this new Dow uranium source data should affect the accuracy of NIOSH's current ER/Appendix
C baseline calculation of the amount of uranium at Dow at the start of the residual contamination period on January 1,
4961. That should in turn affect whether NIOSH has bounded uranium exposures with sufficient accuracy during the
covered and residual contamination periods.

FUSRAP (U.S. Army Corps of Engineers [USACE] and ORNL) in 1999-2000 found mixed uranium and thorium dust in the
rafters above the nine extrusion presses in Building 6, the Dow extrusion building. For some unknown reason, residual
uranium was not surveyed by USACE at that time in the other Dow buildings where MCW/AEC rod straightening
occurred. Pangea Group later found large amounts of residual thorium throughout the Dow complex during 2003-2007
before the thorium license was decommissioned and the license was terminated by IEMA/NRC by a letter dated 6/8/2008
from IEMA Director Velasquez to the President of Spectrulite, Inc.

| will appreciate being notified by NIOSH, the NIOSH Docket office, and by the Board that this new information has been
received and distributed appropriately.

Sincerely yours,

Submitted by Dan McKeel


NOTICE
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vorenrion, J Fvys Joy suotpuoD SurwssadQ



VI-89

On « number of occasions, there has been severe blowing back through the Micronizer feed
funnel ac fairly frequent and regular cime intervals. In some cases this problem has been bad
enough to force continuous readjustment of operating conditions. At other times, only relatively

minor puffing at the Micronizer feed funnel has been observed.

Contamination problems have stemmed from the difficulty of completely cleaning the equipment
between runs of different material. There has been some contamination due to erosion of the
liner material in the grinding chamber and possibly at the metal parts in the dust collection
equipment. Figure 4 shows pictures of the cop and bottom plate liners when new and after

grinding 2500 pounds of material in an operating time of about 100 hours.

There was a constant increase in pressure drop chrough the product filter bag, with no noticeable
effect on the particle diameter or the production rate, until a value of 4 inches of water was
reached. At this point, feeding difficulties forced replacement of the bag. Figure 5 shows the
pressure drop through a new, woot felt filter bag versus pounds of micronized product through

the collector.
Discussion of Results

It appears that the principal cause of blowbacks is instability and unreliability of the vibratory
feed mechanism. The Syntron FM-0-10 is a volumetric feeder whose capacity is too high to
maintain the constant, low weight rates desired. It has been observed that high production
rates permit injector air pressure to be lowered byt increase the tendency to blow back and
chat rates which are too low require an excessive injector air pressure to prevent puffing. An
increase in injector air nozzle diameter would probably reduce feed problems but would also
require more air capacity. A smaller diameter in the feed vencuri tube would also help the feed
situation, but might increase erosion of the venturi tube with consequent contamination of the

product.

It is indicated in Table I chat there was considerable variation in the feed rate for the same feed
material at identical Syntron settings. Runs 10, 11, and 13 should be noted in particular. The

feed rate variation was even greater in the calibration runs as noted in Table II.

It is also indicated in Table I that there is no apparent correlation between the feed rate and the
final product particle diameter within the range tested. Table III indicates a wide variation in

product particle diamerer at a given feed rate.



VI-84

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Recycle
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SCHEMATIC OF pH-METER TEST STAND IN THE PILOT PLANT



V-54

None of the graphite follower blocks crushed sufficiently to free the rods from their butts,
and shearing, with the single-acting shear attached to the press, was necessary in every
case. The behavior of the Grade AGR graphite as a follower block material was not

found to be materially different from that of Grade CS 312.

In the punching experiment the piercing plug was not quite separated from the billet, as
shown in Figure 5, but this was probably due to the graphite piercing cap crushing and
flowing through the opening in the billet without pushing the plug free. A total thrust of

1200 tons was used in the piercing operation.

The uranium follower block used with the billet which was three-fourths extruded was
pushed into the back end of the billet and metal was also back extruded around the follower
block, as shown in Figure 6. An unusual flow pattern, shown in Figure 7, was revealed

by radiographic inspection.

The billet which had only one inch of its length extruded was not completely upset. It
was barrel shaped and exhibited deep longitudinal fissures, apparently indicating that the
billet was too cold and the surface was actually in the beta phase. The temperature
record indicated that the Rayotube was not functioning properly during the heating of this
billet, and the surface temperature of the billet just before it entered the container was
below 1400°F, which is the bottom of the range of the optical pyrometer used.

The chrome carbide die was damaged considerably during this campaign, evidently by the
shearing operation, but enough of the land was intact around the entire ID for it still to

be usable.

- Discussion of Results

No correlation could be drawn between yield and follower block contour, or billet angles,
for the billets extruded with contoured graphite follower blocks. This was probably due
to the wide divergence in transfer times for these billets. The "reverse pipe” defect
observed in the rods with low yields indicates that the cylinder-cone volume ratios on

the billets used were too great.

The punching experiment was considered succesSful, in general. However, the amount of

thrust required indicated that the full thrust of the Weldon Spring press would be required

for punching.



VII-96

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l 20°
2 25°
3 30°

FIGURE 5

FOLLOWER BLOCK



Billet-to-Rollable-Rod Yield, per cent

PIGURE 2

BILLET-TO-ROLLABLE-ROD YIELD VERSUS RATIOS OF CYLINDRICAL-TO- CONICAL VOLUMES
OF BILLETS HEATED IN OPEN-END CANS,
NINTH GAMMA EXTRUSION CAMPAIGN AT BBC IN ADRIAN, MICHIGAN

a
86.0, 4
85.0
Legend

84.0] megene

0-2 1/2-in.-Deep Follower Block

X-3—--in.-Deep Follower Block %
83.0} 4-3 1/2-in.-Deep Follower Block

¢@-Cleaned Dummy Block

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5-0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 1b.0 15.0

Ratio of Cylindrical Volume to Conical Volume



V-78

Dimensiona In Inches

1 4-1/2 vhiei/ 3-1/2

A\

FICURE 15

GROOVED, CONTOURED GRAPHITE FOLLOWER BLOCK



VI-88

100.0

WAPD-Type U0z Feed Rate, 1b/br

1.0

0.40

FIGURE 3

WAPD-TYPE UO2 FEED RATE VERSUS SYNTRON SETTING

L © - Calibration Runs
L- %- Production Runs
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x 8
r “
L j 5
x °o
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Syntron Setting



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The 2.6-in:-diameter piercing mandrel, which was used to free Rod 6 from its butt,
indeored the back end of the rod co form a tube. Continuing pressure on the back end of
the rod caused this tube cto break in tension, with part of it remaining integral with the
rod and part remaining attached to the butt. That part of the tube integral with the rod

is included in the cropping loss for Rod 6 in Table VIII, and that part remaining attached

to the butt is included in the corresponding butt and oxidation loss.
Radiographic inspection of Rods 9 and 11 is: not yet complete and will be reported later.

The chrome carbide die was severely damaged during this campaign. The damage was

quite obviously due co the action of the single-acting shear used.
Discussion of Results

Ic would be necessary to heat copper or cast iron follower blocks to considerably higher
temperatures than those employed in this campaign in order to partially extrude them
behind the rod.

The low yield for Rod 6 was partially due to the 2.6-in.-diameter mandrel indenting the
back end of the rod and forming a tube. The back ends of Rods 7 and 10 were flat, and
the yields were probably raised by inclusion of the center portion of the bute in the back
end of the rod. No extrusion defect was revealed by cropping of Rod 7 and only about
2% of the 3.6% cropped from Rod 10 showed extrusion defect. Therefore, the yield for
these two rods actually was about 91%. It is of interest to note that the yield for

Billet 10, which had a flat back end but was extruded with a contoured follower block,
was approximately the same as that for No. 7, which was a contoured billet. Refinement
of the punch design is necessary to reduce the considerable amount of time consumed

in removing the mandrels from the butts after punching.
Conclusion
Punching shows definite promise as a method for separating rods from their butts.

A considerable amount of work will be required on metal follower blocks if their use is
to be made practicable for freeing rods from their butts. Also, their use would be
economical only if the cleaner operation resulting were deemed highly desirable.



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VII-101

Boule 19 was grown from pure pot-denitrated UO,. X-ray analysis of the resulting boule showed
that the composition of the product lay somewhere between UO,i99 and UO, 9; This shows that
the flame fusion process can be used to convert UO, powder into a solid piece of bigh purity

UO, in one operation.

Work on this project will continue.



-26

%
oa fa[i- tech free}

where
Ds * diameter of shell, inches,

d° = diameter of mandrél, inches, with subscripts L and T denoting diameters at L
and the top, respectively, and

L = distance measured from top of mandrel, inches,
Py = pressure at top of bed, psi,

p, ~ fluidized density, Ib/cu in.

Table IV

Dimensions of Tapered Mandrel

Distance Diameter
Down from Top of Mandrel
inches __inches
0 0:63
5 1.21
Mu 1.61
7 1.91
23 2:14
29 2.34
35 2.50
41 2.65
47 2.77
53 ~ Bottom 2.89

A fluid-bed reduction reactor will be fabricated with a 5-inch-diameter cylindrical shell, a bed
height of 4 ft, 5 in., aad an internal mandrel with the dimensions listed in Table IV. With this
basic equipment the feasibility of the cylindrical-shell, tapered-mandrel fluid-bed reactor will

be investigated.



IM-22

The equations used to compute the size of the conical bed ace straightforward, although
somewhat approximate. For a constant velocity at any point in the bed, the shell caper would be
slightly parabolic. The simplification resulting from the assumption of a linear taper is

accurate enough for scoping purposes, however. The equations are

1) V_ = volume of reactor a >, + 5, +V85)).

s

- Te x 247, 2
2) 8S, - 3600 “% Gor“ P,* U
ys. - Oe Tex Mx 1,
B 3600 492 «Pp =U

4) Pa" Py + AP,

5) P * —yqq- '

where
R= feed race, Ib UO,/hr,
~ desired turnover time, hr,
p, ~ fluidized density, Ib/cu ft,
= height of reactor, ft,

= free cross-sectional area, sq ft,

h
Ss
Q = fluidizing gas flow, SCFH,
T, TM temperature of bed, °R,

P « pressure, psia,

AP = pressure drop across bed, psi,

U = actual superficial fluidizing velocity at bed conditions, ft/sec,
Subscript B = bottom of bed,

Subscripe T = top of bed.

By setting R ~ 80, 0= 2.5, p, “ 237, T, ~ 1510, Py ~ 15.7, and U = 1.8, the following final

equations were evolved:
6) Sp = 4.45 * 107°Q,

DS * 6.96 «107 S ,



IV-34

Table.VI

Spectrographic: Analysis of Powder from Off-Gas Header

Constituent Results,
Ni Weak-Moderate
Fe Weak-Moderate.
Cr Strong:
Mo Strong:
v Moderate Composition of
Si Very, weak-Weak Hastelloy’ ¢
Ma wee
Mg Very ‘strong
U Very ‘strong
v Moderare-Strong

The holdup.in this reactor was measured after Run 6 and found tobe 100 pounds of slag.

The Hastelloy C reactor screw was removed after $3 hours’ operation at 6 rpm. At some point
during this period the: sctew shaft was broken at the butt-weld as indicated by scale formation
on each face of the break. There was only minor.evidence of erosion or corrosion on the five-
foot section of the screw from the drive end to the butt-weld; however, the erosion or corrosion
from the butt-weld to the powder discharge port was very severe.

Table VII gives the thicknesses of various disks cut from the reactor tube. ' The original plate
was one-quarter-inch plate but external gussets probably cut from the-same:plate measured 0.241
inches.

Table VII

Reactor Wall Thickness after $3 Hours’ Operation

Thickness
Position in. :
One Foot from Discharge-End, Top _ 0.200-0:206
One Foot from Discharge End, Bottom 0.215-0.217
One Foot from Feed End, Top. 0.217-0:217
One. Foot from Feed End, Bottom © 0,213:0:213
Discharge End. by Flange 0.220

Feed End by Flange: 0.221



V-58

The unusual flow pattern in the billet that was three-fourths extruded is not readily
explained but may have been due to the interior of the billet and uranium follower block being
hotter than the surface. This flow pattern was similar but not identical with that

observed in rods extruded from flat-end billets with contoured graphite follower blocks.
The information regarding flow available from the billet extruded only one inch could

not be considered reliable because of the low billet temperature.
E. Conclusions

Further efforts toward increasing yields by the use of contoured billets and contoured
follower blocks should be directed toward greater cylinder-cone volume ratios on the

billets.

The punching process showed promise as a means of separating the rod from its butt, if

the full capacity of the Weldon Spring press could be exerted on the mandrel.

Grade AGR graphite showed no more promise than Grade CS 312 as a follower block

material that will crush and free a rod from its butt.
V. Eighth Campaign at Dow
A. Purpose

The primary purpose of this campaign was to develop a method for separating a rod from
its butt without the use of a saw or shear. The two methods investigated were punching

and the use of metal follower blocks. The reasoning behind the latter approach is:

(1) :if the concour of a metal follower block is such that the interface between the back
end of the rod and the follower block is flat after extrusion,

(2) if no welding takes place between the rod and the follower block, and
(3) if the follower block is partially extruded, then

(4) the rod would separate freely from the follower block and the resultant yield should
be high.

Contoured copper, cast iron, and uranium follower blocks, having various contour depths,

were used.



V-76

Extrusion of the tapered billet, No. 9, was accomplished with no difficulties.

After inserting Billet 7 into the container with the follower block arrangement shown
in Figure 12, the ram was advanced until pressure was indicated on the gauge and
then one inch further. The upset billet with its 6 inches of rod projecting was then
removed from the container in the box specially designed for this purpose, which was

also used in the seventh campaign.

Billets 8 and 10 were extruded with grooved graphite follower blocks of the design
shown in Figure 15. The design of these follower blocks was based on the expectation
that the graphite near the edge would crush and flow into the groove cavities, allowing
the uncrushed center portion to be forced through the die as a punch. These follower
blocks did not crush in such a manner as to free the rods from their butts, so che rods

were sheared.
Rod Evaluation

All rods except No. 7 were evaluated according to the procedure described for the
seventh campaign above. The partially extruded billet, No. 7, will be sectioned,

etched and radiographed for examination of the flow pattern in upsetting.

C. Experimental Results

Yields for the individual rods are listed in Table XI.



IV-28

The immediate program is concentrated on the feasibility of recovering the uranium from slag in

a screw reactor.
Experimental Equipment

The green salt reverter at the St. Louis Production Center was modified for this fluorination

work. A sketch of the modified equipment is shown in Figure 1. The reactor consists of a
ten-foot-long, eight-inch-diameter Inconel tube provided with a ten-foot-long ribbon type screw.
The screw consists of three 1-inch by °{,-inch Hastelloy C ribbons connected by Y-supports to

a 4,-inch-diameter shaft, and was fabricated in five-foot sections, then bute-welded at the center.

It is rotated by a variable speed drive and is free floating at the idle end. This reactor is enclosed
in a 30-kw electrical furnace divided into three zones of 10 kw each. Slag is fed from a 300-pound-
capacity feed hopper, through a two-inch-diameter feed screw, to the drive end of che reactor.
Fluorine, supplied in 400-psi cylinders, is fed through a modified Matheson Type I5A gas pressure
regulator and a Pyrex rotameter, to the reactor countercurrent to the slag flow. The UF, produced
and the off-gases are vented to the low-pressure scrubber system where they are neutralized with
lime. The fluorinated slag is discharged into a receiving hopper, then emptied through a two-inch-
diameter discharge screw and a cooling screw to a packaging station after each run. Nitrogen is
available for purging the reactor and the fluorine manifold. The pressure at each end of the
reactor is measured by means of a manometer filled with a fluorinated hydrocarbon oil. Each of
the three electrical heating zones is controlled from a temperature indicator-controller with its
thermocouple between the reactor tube and the furnace elements. Thermocouples are also

provided on the reactor wall near each end of the tube and these temperatures are read on a

temperature recorder.
Experimental Procedure

The operating procedure was as follows: The slag feed hopper was filled wich slag and enough
slag was added to the receiving hopper to provide a gas seal. The empty reactor was purged with
nitrogen and preheated to operating temperature. Fluorine flow was then started and, as soon as
the reactor screw was rotating, the slag feed was started. At the end of each run the slag feed
and the reactor screw were stopped, the fluorine flow was cut off and the reactor purged with
nitrogen for several hours. The slag in the receiving hopper was discharged to the packaging

station leaving enough in the receiver to provide a seal for the next run.

Table I gives the operating data for the eight runs made in this reactor; the first six runs were

made using normal MFL as feed and the last two runs were made using RMF dust.



VII-94

am Ss

a|

FIGURE 1
GROWING A URANIUM DIOXIDE BOULE BY THE FLAME FUSION PROCESS

<|



9 and 10

GENERAL SUMMARY

Work was continued during this quarter on the recovery of uranium from slag, the gamma extrusion
of uranium, and on fuel element studies. The results of an investigation on automatic control of
neutralization of raffinate, and ofthepreliminary design of a pilot-plant UO,-reduction fluid-bed

reactor are reported.

Specific studies are summarized as follows (Roman numeral refers to the section on which the

summary is based):

Il. Based on experimental studies in the pilot plant, a proposal is presented for the use of a pH

meter co control automatically the addition of lime in the neutralization of raffinate.

III, Design calculations have been made for a continuous pilot-plant fluid-bed reduction reactor

of tapering cross-sectional area to handle 50 pounds per hour of fluid-bed-denitrated UO,.

IV. Tests in an eight-inch-diameter screw reactor showed that the uranium content of MFL could

be reduced to 0.15-0.20% by treatment with fluorine at elevated temperatures.

V. Evaluations at Bridgeport Brass Company of die materials for gamma extrusion of uranium
have confirmed that sintered chromium carbide dies attain excellent die life and provide
good extruded surfaces. Concave-faced graphite follower blocks have not improved the

yield in gamma extrusion when used with flat-faced billets.

Studies conducted at Dow Chemical Company of special follower blocks confirm that contour,
temperature, and material all require careful selection for achievement of optimum metal yields.
Full-sized carbide dies have produced good extruded bar surfaces but require care in bute
severance to avoid damage by shear blades. Separation of the butt without need for shears or
saw has been shown to be feasitle by ‘penetrating the butt with a circular punch slightly

smaller than the die opening.

VI. WAPD-grade UO, was ground to an average particle size of 0.8 micron in an eight-inch-diameter

Micronizer at production rates between 20 and 50 pounds per hour.

VII. Fusion in an atomic hydrogen arc shows promise as a method for growing single crystals of

pure UO, for fuel element use, employing either UO, or UO, powders as starting materials.

Laboratory work for this quarter has been reported in Part I as a separate volume.



V-77

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VI-83

In a standard Micronizer of this size, there are six grinding jets set tangentially to a 5 Y4-inch

circle. The pilot plant unit has an additional six jets set tangentially to a 64-inch circle.

The solids feed system consists of a one-eighth-inch nozzle discharging into a one-half-inch

venturi tube directly undet the Micronizer feed funnel.

Auxiliary equipment is shown in Figure 2 and includes an air compressor, an air receiver,
a-vibracor fedder:(Syntton), 4 product bag ‘filter; a product rotary valve,‘a product

drum, and a dust collection system which includes a bag filter, rotary valve, and scrap drum.
The compressor is a carbon ring machine with a maximum pressure rating of 135 psig and a

capacity of 130 SCFM at 100 psig.

The Micronizer is fed by a Syntron, Model FM-0-10, vibratory feeder discharging into the feed
funnel. Feed rate adjustments ace made by changing the amplitude of the vibrations applied

to the feed trough.

The grinding air passes from the Micronizer through a ten-square-foot, felt, product filter bag.

The product is then discharged through a rotary valve to a packaging drum.

There is, in addition, a bag filter located outside the building which serves a hood in the

Micronizer enclosure and collects extraneous dust.
Experimental Procedure

Materials micronized so far include fluid-bed-denitrated UO,, pot-denitrated UO,, MCW-produced
UF,, and WAPD-grade UO,.

All operations have been made with all twelve grinding jets installed in an effort to attain finer
grinding. Smaller jets are used in order to maintain the flow rate and pressure drop that would

occur with six standard jets.

Grinding pressures have been in the range, 90 to 100 psig, with most of the runs at the higher
figure. Air flow rates at these pressures are about 120 cubic feet per minute. The solids feed
injector air pressure is ordinarily set at the lowest value consistent with smooth operation and
has ranged from 40 to 80 psig depending on the feed rate and grinding pressure. Feed rates
have been varied from about twenty to fifty pounds per hour with the usual rate at about twenty-

five pounds per hour.



Reporte Number: MCW-1416 Subject Category: Technology - Feed Materials
Date of Issue: August 1, 1958 Title: PROCESS DEVELOPMENT QUARTERLY
REPORT, PART II - PILOT PLANT WORK

Internal Distribution

No. of Copies

Dr. N. E. Berry 1
Mr. B. J. Bunez

Mr. K. J. Caplan
Mr. F. R. Dowling
Mr. R. M. Edwards
Dr. P. J. Fain

Dr. R. H. Fariss

Dr. J. A. Fellows
Dr. C. D. Harrington
Mr. R. F. Hartmann
Dr. J. A. Kennelley
Mr. H. C. Kloepper
Mr. J. T. Krieg

Dr. C. W. Kuhlman

Mr. G. P. Lang
Dr. F. J. Ludwig

Metal Pilot Plant Files
Mr. E. I. Miller

ome omr momen ae eee aro ae eee a i a a roy

Dr. J. P. Morgan
Dr. D. E. Morris
Mr. H. Myers

Mr. J. A. Nelson
Dr. N. F. Neumann
Mr. W. G. Perty

Dr. W. C. Philoon
Mr. R. D. Piper

Dr. W. J. Robertson
Mr. A. E. Ruehle
Mr. E. F. Sanders
Dr. J. U. Shepardson



VI-81

PREPARATION OF MICRONIZED URANIUM COMPOUNDS

by

W. J. S. Smith

Summary

Approximately 2000 pounds of WAPD-grade UO, has been ground to an average particle diameter
of 0.8 microns in a fluid-jet grinding mill. There was no apparent correlation between the
product particle diameter and the feed rate within the range of 20 to 50 pounds per hour.
Instability and unreliability of the vibratory feed mechanism resulted in considerable variation

in the feed rates and numerous powder “blowbacks” through the feed system.
Introduction

Very finely ground materials are occasionally required for investigation of the processes employed
in uranium production. This report is concerned with the development of operating technique and
the evaluation of performance of a fluid-jet grinding machine, the Micronizer, manufactured by the

Sturtevant Mill Company, Harrison Square, Boston 22, Massachusetts.
Experimental Equipment

The Micronizer (Figure 1) consists of a shallow, circular grinding chamber with such necessary

connections as grinding fluid inlets, a feed introduction point and a product discharge line.

Grinding of materials in the Micconizer results from the action of high velocity gas streams
emerging from nozzles spaced around the periphery of the grinding chamber in which there is a
circulating load of the solid to be ground. The compressed gases issuing through these jets
maintain a high speed of rotation in the grinding chamber. Solids fed into the grinding chamber
are accelerated by the rotating gases and are thrown to the periphery where a portion coming into
the zone of action of a nozzle is further accelerated tangentially and radially inward, causing
violent impact between the particles thus accelerated and other particles circulating at a much
lower velocity in a thin band near the periphery. The fines resulting from the continuing series
of impacts are carried by the rotating gases in an inwardly spiraling pach toward the central
outlet. Thus, the mass is subjected to an intense classifying action and, as the fine particles

approach the outlet, centrifugal force returns the oversize particles co the grinding zone.

The Micronizer installed in the pilot plant has a grinding chamber eight inches in diameter by
1% inches deep. As shown in Figure 1, all parts in contact with the product are lined with

Linatex, a tough rubbery material highly resistant to abrasion.



VI-92

Conclusions

Approximately 2000 pounds of WAPD-type UO, has been micronized to an average particle
diameter of about 0.8 microns at production rates of about 20 pounds per hour at a grinding
pressure of 100 psig. These values are of the same order of magnitude as those reported
previously,'"? the differences possibly being due to bias in the Sub-Sieve Sizers or to differences
in sampling technique. Further work will be directed toward developing maximum capacity in

the Micronizer while maintaining grinding efficiency.

In order to minimize contamination of material for which there are tight purity specifications, the

equipment must be completely disassembled and thoroughly cleaned before grinding operations

are begun.

The production rate has been limited by feeding problems. Attempts to solve these will be made

by modification of the Syntron feeder and of the solids injection system.

' Henderson, C. M., Wrinkle, R. B., Process Development Quarterly Report, Part I, Mallinckrodt Chemical Works,
MCW-1400 (February 1, 1957), p 129
? wrinkle, R. B., Hendetson, C. M., Process Development Quarterly Report, Part Il, Mallinckrodt Chemical Works,
MCW-1402 (May 1,'1957), p 151



Vv-60
Table VI
Constant Extrusion Conditions - Eighth Gamma Extrusion Campaigo

at Dow, Madison, Illinois

Billet Temperature 1850°F

Hot Follower Block. Temperature See Table VII

Warm Follower Block Temperature 900°F

Tool Oven Temperature 890°F

Container Temperature 850°F

Die Material
Billets 6, 7 and 10 A.LS.I. T-1, 50°54 Re
All Other Billets All, Lud. Grade CA815

Chrome Carbide Insert
(in A.LS.I. H-13 Case, 50-54 Re)

Die Design
Billets 6, 7 and 10 Flow Type, %-in. inlet radius, %-in. land

All Other Billets Shear Type, 1-in. land.



V-56

Figure 5

Pierced Billet from Punching Experiment, Billet No. 6,

Seventh Campaign at Dow

Figure 6

Butt from Partially Extruded Billet, Billet No. 4,



I-18

consumption, but are difficult to design and operate because of the tendency of the gas to short-

circuit through the plate-to-plate downcomers.

To counter this disadvantage of the fluid bed, investigators at Y-12 have developed the tapered-
shell fluid bed.**? By providing a reactor cross-section which varies with the height of the bed,
it has been possible to keep the fluidizing velocity approximately constant throughout the bed.
(In a cylindrical bed it will be recognized that friction losses cause a reduction in pressure and
a consequent increase in velocity as the gas rises through the bed.) If the gas velocity is kept
within a narrow range about that which defines incipient fluidization, turbulent mixing in the bed

is virtually eliminated. The vertical solids movement closely approximates “piston” flow.’

There are other advantages which the tapered bed has over a cylindrical bed. Solids elutriation
is less, and greater height-to-diameter ratios can be employed without disastrous slugging in
the upper portion of the bed.

However, the tapered shell is difficult to fabricate and lacks flexibility. If gas flow rate,
particle size, or temperature are changed, the tapered bed no longer assures low solid mixing
rates; turbulence in the bed will increase as the difference between design and operating

conditions becomes greater.

As an alternative to the tapered shell, it is possible to use a tapered mandrél, installed in a
cylindrical shell. This mandrél would be designed for constant gas velocity through the bed,
and thus should duplicate the fluidization characteristics of the tapered shell.

The obvious advantage of the mandrél design is versatility, since replacement of a mandrel with
one of different taper is easy. A mandrel should be inexpensive to fabricate. Further, a mandrel
would offer an excellent method for internal cooling of the bed.

Preliminary Design Calculations and Discussion

Scoping calculations have been performed to determine the dimensions of a pilot plant fluid-bed
reactor for the reduction of fluid-bed-denitrated UO, according to the reaction
uo, + H, —® UO, + H,O. Results of these calculations are presented in this report.

+ Uranium Chemistry and Analytical Development Excerpts from Y-12 Plant Quarterly Report, First Fiscal Quarter,
1938, Union Carbide Nuclear Company, Y-B65-169 (November 22, 1957), p 8-10

2 Uranium Chemistry and Analytical Development Excerpts from Y-12 Plant Quarterly Report, Second Fiscal Quarter,
1958, Union Carbide Nuclear Company, Y-B65-191 (February 26, 1958), p 15-18

* y-B65-191



V-47

5. Evaluate National Carbon Co. AGR Grade graphite as a follower block material.
6. Evaluate a seven-inch-ID shear-type chrome carbide insert die.

B. Experimental Work
1. General

Constant extrusion conditions and those for individual rods are shown in Tables III

and IV, respectively. Truncated conical contours, designated by the angle at the base
of the cone rather than by the depth of follower block contour, were machined on the

back ends of the billets for follower block contour evaluation and for partial extrusion.
AGR Grade graphite follower blocks of the design shown in Figure 3 were used for
follower block contour evaluation. Uranium follower blocks, of the same design as Figure 3
but with the same diameter as the billets, were used for partial extrusion to give as

nearly as possible ideal flow conditions.
Table Ill

Constant Extrusion Conditions -
Seventh Gamma Extrusion Campaign at Dow, Madison, Illinois

Billet Temperature 1850°F

Container Temperature 890°F

Tool Oven Temperature 900°F

Hot Follower Block Oven Temperature 1850°F

Warm Follower Block Oven Temperature 910°F

Follower Block Material Grade AGR Graphite
Follower Block Design See Figure 3

Die Material
Billets 1-4 and 7-10 All. Lud. Grade CA815
Chrome Carbide
Insere (in A.LS.1. H-13 Case, 50-54 Re)

Billet 6 A.LS.L. TI, 50-54 Re
Die Design
Billets 1-4 and 7-10 Shear Type, 7-in. ID, I-in. land
Billet 6 Flow Type, 7-in. ID, %-in. inlet radius,
Yin. land
Container Liner ID 17 in.

Reduction Ratio 5.9 tol



V-51

pressure was indicated on the gauge and then advanced eight inches more to extrude
three-fourths of the billet: Thecrod ani bute were removed from the press intact and covered
with salt. For the second billet, the ram was advanced only one inch after pressure
was indicated on the gauge, with the result that only about six inches of rod was
extruded. This biller was removed from the container in a box specially designed for

this purpose and then covered with salt.

Since neither a shear nor a saw fits readily into the design of the press at Weldon Spring,
and graphite follower blocks of the design and material used thus far have not crushed
in the manner desired, the need for an alternate method for freeing rods from their butts
arose. A method, termed “punching,” was envisioned for this need which would consist
of forcing a mandrel of slightly smaller diameter chan the die through the butt, thus
piercing a hole through the butt and pushing the back end of the rod through the die. As
a preliminary investigation of this process, a short billet was pierced, or “punched,”
during this campaign. The five-inch-long billet for this “punching” experiment was
inserted in the container, as shown in Figure 4, with a hollow graphite follower block
behind it. A flat steel “pusher plate,” screwed into the mandrel, was used to push the
billet to within about one inch of the die. The ram was then withdrawn, the “pusher
plate” removed, and the graphite piercing cap inserted in the mandrel. The ram was
advanced until the front of the piercing mandrel was about one inch beyond the face of

the die, piercing the billet as shown in Figure 4.

A shear-type chrome carbide insert die was used for all billets except the punching

experiment. A steel flow-type die was used for this billet.
4. Product Evaluation

The rods extruded with contoured graphite follower blocks were washed free of salt,
weighed, cropped, reweighed and examined visually for yield determination. One-inch-
thick longitudinal slices, 90° apart, were cut from the butts of the partially extruded
billets, and radiographed. A number of one-inch-thick traasverse slices, cut from the
back end of the rod from the billet which was three-fourths extruded, were also

radiographed.
C. Experimental Results

Yields for the rods extruded with contoured graphite follower blocks are listed in Table V.
All of the surface area of these rods was of a quality satisfactory for rolling. However, the
surfaces of the rods extruded from the 16%-inch-diameter billets were slightly superior to
those extruded from the 15'4-inch-diamerer billets. The type of “reverse pipe” back-end
defect encountered in rods extruded from flat back-end billets and contoured follower blocks

in the sixth campaign was also evident in those rods from this campaign which had low yields.



V-80

- Conclusion

Use of a punching procedure similar to that used in this campaign is planned in the
Weldon Spring operation and should be satisfactory. Differential hardening of the punches,
to give maximum hardness on the front end and a much lower hardness on the shank end,

should decrease the danger of punch breakage.

No difficulties should be encountered in using the tapered billets contemplated for
Weldon Spring.



H-13

Experimental Procedure

Two battery-operated Beckman pH meters were used during the test. One was included in the
continuous monitoring system and the other was kept in che pilot plant laboratory and used under
carefully controlled conditions. The two instruments were standardized against the same buffer
solution and checked for proper operation daily. Readings were made of the pH on the
continuously measuring instrument hourly during the day shift and a sample of the material was
taken at the same time for pH determination on the bench meter. During operation, raffinate flow
past the electrodes was regulated at five ft/min to prevent scaling. Erosion of the electrodes
could not be detected at this flow rate. The electrodes of the continuous meter were in contact
with stagnant raffinate each night co simulate refinery conditions while the electrodes of the bench
meter were kept in distilled water.

Results and Discussioo

A comparison of continuous versus “bench” pH measurements is shown in Table I.
Table I

pH of Refinery Raffinates®

Continuous Beach
Measurement pH Meter pH Difference

8.35 8.30 +0.05
8:40 8.25 +0.15
8.30 8.20 +0.10
8.30 8:20 +0.10
8.30 8.20 +0.10
8.20 8.15 +0.05
8.20 8.20 0.00
8.25 8.15 +0:10
8.25 8:40 -0.15
8.25 8.65 -0.40
8.15 8.30 -0.15
8.20 8.20 0.00
8.20 8.25 "-0.05
8:10 8.20 “-0.10
19 8.0 -0.10

. 7.8 8.0 -0:20

“These figures comprize a representative sample of the total data; one hundred and three
@ measurements were made in all.



[ Container

Die ——}

Dummy
Block

IN
7 44

— Pusher Plate

7;

Billet

Hollow Follower Block

Inserting Billet Into Container

LLL.

hs

wen VANES
Plug Ly i \
7. VV A

Graphite Piercing Cap

Piercin, eration

FIGURE 4

PUNCHING EXPERIMENT





V-72

2 ine 2 in,

a

b
Hollow Plugged

T 10° t 20°
£

7
1 8

e
Solid Solid Solid

1/2 in 4 in. 2 in,

All Follower Blocks 17 in. Diameter
2-in.- Diameter Flat Ac Bottom Of All Contours
Plugs Slide Fit In Follower Blocks

FIGURE 11

GRAPHITE FOLLOWER BLOCKS, NINTH CAMPAIGN AT DOW



1V-27

URANIUM RECOVERY FROM SLAG

by

H. F. Plagens
E. F. Sanders

Summary

Eight slag fluorination runs have been made in an eight-inch-diameter screw reactor. In general,
the resules indicate a final uranium content in fluorinated MFL of 0.15-0.20% U regardless of the
operating conditions or sieve fraction within the range tested. A slag feed rate of 100 Ib/hr was

attained with a retention time as low as one hour and a fluorine excess of 1.4 times theory.
Introduction

One of the products of the reaction between uranium tetrafluoride and magnesium is magnesium
fluoride slag. This slag contains small amounts of metallic uranium and uranium oxides as a
result of incomplete separation of uranium products from the slag during the reaction. In the
dingot process a portion of this by-product slag is recycled for use as a refractory while the other
portion is discarded; however, because of the value of the contained uranium, it is desirable to

recover this uranium from this reject stream before it is discarded.

The general objective of this project is the establishment of a process for converting the contained
metallic uranium and uranium oxides to uranium hexafluoride. In this process fluorine is

continuously allowed to react with the contained metallic uranium according to the equation
Voy + 3Figy * UF cay»

and with other forms of uranium in accordance with similar equations. The gaseous uranium
hexafluoride product is condensed from the off-gas stream and can either be used as feed material
for the cascade or reduced co uranium tetrafluoride for conversion to uranium metal. This
fluorination process has several significant advantages over the other techniques for recovering
the uranium from slag. Some of these advantages are:

(1) the elimination of the usually required slag pretreatments;

(2) easy separation of the uranium from the slag since the uranium is removed in the vapor

phase;

(3) the direct conversion of the uranium to a usable form thus eliminating the necessity for

reprocessing, such as reintroduction into the refinery; and

(4) modest equipment requirements since the conversion and separation are done in one step.



V-70

15-1/4
in.

10°

15-3/8
in.

16-1/4

in.

FIGURE 9

MACHINING OF DINGOT NO. 212



V-63

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CF |

Follower Block ~e| Je 3-5/16 in,

-1/16

in
bh A —e

17 +0

i

in
T

cy a

4

10°

{ o
T

Follower Block Plug ch

Dimension, in.

Item Part A B c

Fol. Block 2-5/h

2 | Fol. Block | 7
3 Plug 2-3/4 2-1/16
4 | Plug 1 2-7/16

Item 3 Must Be Slide Fit in Item 1
Item 4 Must Be Slide Fit ta Item 2

FIGURE 8

FOLLOWER BLOCKS IN PUNCHING EXPER IMENT



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V-37

GAMMA EXTRUSION OF DINGOT METAL

by

T.N. Dean
W. E. Ellerman

I. Summary

Four gamma extrusion development campaigns are reported, one from the program at BBC,

Adrian, Michigan, and three from the program at Dow Chemical Co., Madison, Ilinois.

A. Ninth Campaign ac Adrian

1.

No correlation was found between yields and follower block contour, using flat-ead
billets and contoured graphite follower blocks having respective contour depths of
2%, 3,and 3 Yinches.

Chrome carbide was confirmed as an excellent die material. At the conclusion of this

campaign, 47 rods had been extruded through the die employed and it was still usable.

B. Seventh Campaign at Dow

1.

No correlation was found betweea yields and follower block contour, using contoured
billets with contoured foilower blocks having respective cone angles of 20°, 25°, and
30°.

A slightly deleterious effect on rod surface quality was found in increasing the billet

diametral upset from ¥, inch to 1% inches in a 17-inch-ID container liner.

An unusual flow pattern, similar to “reverse pipe,” was cevealed by radiographic

inspection of a billet partially extruded with a uranium follower block.

- A five-inch-long billet was pierced with 1200 tons of thrust, using a seven-inch-ID die,

a 6'°/,-inch-diamecer piercing cap; and a 6 %-inch-diameter mandrel.

Grade AGR graphite follower blocks were not found to be more effective chan Grade CS
312 in crushing and thereby freeing rods from their butts.

A shear-type chrome carbide insert die produced rods of satisfactory surface quality,

but was severely damaged by the action of the single-acting shear used to sever the butt.



V-57

OI6TZ “ON LOONIG ¥Os NWililvd sold

2 zano1a

i “Ur 2/12:

ts uwoqdownw ty Priwoeds3sa)aly
mh
1
‘uy g/T = 3n9 aes



TII-23

8) AP = 1.646h,
9) Py = 15.7 + 1.646h,

4.165
S, + 4.45 x. 10%Q + ¥4.45 x 10S,Q

10) Sg [15.7 + = 6.96 x 107°Q.

For a given value of Q, equation 10) was solved by trial and error. The value of Sy was then
used to compute b and AP.

Case II-A was computed for a fluidizing gas flow of 300 SCFH, the maximum available supply
rate. The shell for Case II-A is too small in average diameter for pilot plant studies, and is too

tall, requiring an inlet gas pressure greater than that which is available.

The resules of the calculations for a cylindrical shell containing a tapered mandrel are presented
in Table IH.



VI-90

Bottom, New Top, New

Bottom, Used Top, Used

Figure 4
Micronizer Plate Liners, New and After Grinding
Approximately 2500 Pounds of UO, in Approximately
100 Hours



V-44

2. Billet Heating

The billets were encased in graphite cans and heated in a gas fired muffle furnace,

as in the eighth campaign.’ Two types of cans were used. One type was of the same
design as that used in the eighth campaign, having one end solid and the other closed
by a plug. The other type was similar but the solid end was replaced by a %-inch-
thick slide-fit disc. The latter design was intended to permit transfer of a billet in

its can to the loading head on the press, where the ram could push the billet directly
from the can into the container liner, whereas the earlier design necessitated

breaking of the can from the billet before transferring it to the press. Seven rods

were transferred as planned in the open-end type can, but operational difficulties
necessitated breaking eight other cans of this type from the billets either on the

roller conveyor or on the table in front of the furnace. Insufficient allowance had been
made for expansion of the billets in the solid-ead type cans and all of these cans burst

io the furnace, permitting some oxidation of the billets.

Plans had called for heating of the graphite follower blocks in the cans with the billets

to minimize transfer time, but the cans were not long enough for this in all cases, so

the follower blocks were heated separately, although in the same furnace. The follower

blocks are shown in Figure 1.

3. Extrusion

The %-inch graphite disc forming the back end closure of the open-end cans was to be
removed by stopping the forward movement of the ram just before the back end of the
billet entered the container. This was accomplished in only two cases (Billets 17 and
27). In the other cases the disc entered the container with the billet and remained

between the billet and contoured follower block during extrusion.

In every case, metal back-extruded past the graphite follower block and adhered to the
face of the dummy block. This metal was permitted to remain on the face of the dummy
block for 13 of the 28 extrusions (Table II), seriously interfering with the intended

function of the contoured follower blocks.

The chrome carbide die used in this campaign had been used for extrusion of one
EZ Hollow cube for NMI, five rods during the sixth gamma campaign, and 13 rods

during the eighth gamma campaign.

* Dean, T. N., ef ale, MCW-1613, p 64-65



VI-85

Experimental Results

The only material on which a significant number of runs has been made is WAPD-grade UO,.
This material is fed as a finely divided, dense powder with a mean particle diameter of about
four or five microns, 100% passing through a twenty-mesh sieve. A summary of operating
conditions and results for the WAPD materia! is presented in Table I. These data are
representative of runs made on all material with a mean particle diameter in the range below

ten microns, including MCW plant- produced UO, and UF,. The feed rate calibrating data for UO,
are listed in Table Il and are plotted, with similar daca from the production runs, in Figure 3.
Table III] shows the Micronizer product particle diameter variation during Run 14. All particle

diameters in the micron range were determined on a Fisher Sub-Sieve Sizer.
Table 1

Micronizer Operation for WAPD-Grade UO,

Product
Collector Mean
Run Production Injector Pressure Product
Run Duration Syntron Race Pressure Drop Diameter
No. Date he:min Setting tb/hr Ib/in.? in. H,O micron
10 6/5 6:55 75 45 50 1.5-2.0 0.81-0.90
ll 6/6 6:55 75 35 60 0.6-1.7 0.74 - 0.86
12 6/9 6:10 70 21 65-70 1.5-2.2 0.81- 0.84
13 6/10 6:30 70 30 65-70 2.2-2.4 0.72 - 0.81
14 6/11 5:15 70 19 65-70 2.3-2.8 0.68 - 0.96
15 6/12 7:30 70 19 70 2.4-3.0 0.74-1.06
16 6/13 7:30 70 20 65-70 2.9-3.0 0.81 - 0.89
7 7/2 4:20 70 21 65 2.4-3.0 0.80
18 3 7:35 70 22 65 2.6-3.3 0.81 - 0.86
19 7/7 8:40 70 23 . 65 2.6-3.7 0.78
20 7/8 7:40 70 24 65-75 3.0-4.0 0.80 - 0.82
21 7/9 7:45 70 17 75 0.6-2.0 0.80 - 0.86



V-62

Billet Heatiog

No difficulties were encountered in billet heating during this campaign. However,
only one coil was used as the one damaged during the seventh campaign had not yet

been repaired.
Extrusion

The follower blocksfor Billets 1, 3, 5 and 8 were of the design shown in Figure 3,
except for the angle on the cast iron follower blocks. They were cast to shape and
the periphery was machined to insure rotundity. The respective angles on the cast
iron follower blocks corresponded to contour depths of 2% inches and 3 inches. The
graphite follower blocks used for Billets 7 and 10 were of the design shown in

Figure 8, and that for Billet 6 was of the same design but flat with a 2.6-inch-diameter
hole and plug. The flat copper follower blocks used with Billets 2 and 4 were five
inches thick. Angles to correspond to the follower block angles were machined on

one end of all of the billets used with contoured follower blocks.

Follower block handling was improved in this campaign by picking up the follower
blocks, from a holding fixture, with che billet grab. Previous practice had been to
place them behind the billet on the loading head at the press, after the billet had

been placed on the head. This improvement resulted in generally shorcer and more

uniform transfer times.

After extrusion of Billee 6 with an articulated dummy block of the type usually used
at Dow, the ram was withdrawn. A separate dummy block having a 2.6-inch-diameter
Piercing mandrel attached was placed on the billet loading head and pushed into the
container by the articulated dummy block. The ram was advanced until the front
end of the mandrel was about 16 inches beyond the face of the die. The mandrel
pushed the graphite plug out of the follower block and pushed on the back end of the

rod until ic was freed from its butt.

The same type of operation was performed on Billets 7 and 10 except that a 6%-inch
mandrel was ‘used and the ram movement during the punching operation was stopped
when che end of the mandrel was about two inches beyond the face of the die. A
thrust of approximately 1400 tons was used in the punching operation on Billet 7.
An attempt was made to stop the advance of the ram when the thrust had reached
250 cons on Billet 10, in order to simulate the thrust conditions of punching with the
piercing ram of the Weldon Spring press. However, the inertia of the massive

crosshead of the 5500-ton press used carried the ram forward until a thrust of



VI-86

Table I

Calibration of Micronizer Feeder with WAPD-Grade UO,”

Time Average

Syntron Duration Feed Rate

Setting min lb/hr
50 12 1.57
50 12 0.68
50 12 0.56
50 12 0.32
50 12 0.17
55 12 1.04
35 12 0.47
55 12 0.27
55 12 0.18
55 12 0.24
60 12 0.89
60 12 0.43
60 12 0.27
60 12 0.20
60 12 0.15
65 12 1.04
65 12 0.81
65 12 0.62
65 12 0.49
65 12 0.46
70 12 1.07
70 12 1.56
70 12 5.19
70 12 5.57
70 12 6.16
75 12 3.35
75 12 10.7
75 12 13.7
75 12 17.0

75 12 19.0



IV-31

Results

The slag feed analyses are given in Table II and the fluorinated slag product analyses are given
in Table II]. Table IV shows the uranium content of fluorinated MFL at various slag feed rates
and fluorine excesses. Table V gives the uranium content of fluorinated MFL for various sieve
fractions. Table VI gives the spectrographic analysis of a sample of powder taken from the

off-gas header.
Table II

Slag Feed Analyses

Component FL RMF Dust
Total U, % 1.50 2.30
Ue, % 0.50 0.50
Unoxidized U, %7 1.40 2.10
ut’, % 0.23 0.35
Free Mg, % 0.12 0.02
MgO,% 3.0 -
H, (as H,O and HF), ppm 41 150
Sieve Fraction

+20 Mesh, % 0.1 1.0

-20 to +40, % 1. 1.0

-40 co +80, % 12.9 0.6

-80 to +100, % 7.0 0:4

100 to +200,°% 21.0 3.4

-200'to +325,°% 12.3 6.5

7325, % 45.6 87.0

@ The term “unoxidized U” as used here denotes uranium with a valency of +4 or less.



CONESRERTTAL

TABLE OF CONTENTS

I- GENERAL SUMMARY
Il - CONTINUOUS pH MEASUREMENTS OF NEUTRALIZED RAFFINATES

Ill - PRELIMINARY DESIGN OF A PILOT-PLANT UO,-REDUCTION
FLUID-BED REACTOR

IV - URANIUM RECOVERY FROM SLAG

V - GAMMA EXTRUSION OF DINGOT METAL

VI - PREPARATION OF MICRONIZED URANIUM COMPOUNDS
VII - FLAME FUSION STUDIES

GLOSSARY OF SPECIALIZED TERMS

7 and 8

Page No.

11

V7
27
37
81
93

103


V-46

No definite correlation was found between yields and depths of follower block contour
or cylindrical-conical volume ratio. A greater effect from cleaning of the back extruded
metal from the face of the dummy block is indicated in Figure 2.

Only five billets were handled in the preferred manner, #.e., heated in open-end cans and
extruded with clean dummy blocks. Two of these were extruded with 2 ',-inch-deep
follower blocks and three with 3 4-inch-deep follower blocks, resulting in average yields
of 82.4% and 82.1%, respectively.

No consistent effect on yield was observed from the %-inch graphite discs between five

of the billets and their follower blocks.
E. Conclusions

No correlation was found between yield and depth of contour, using contoured graphite
follower blocks and flat back-end billets, and cylindrical-conical volume ratios between
5:1 and 15:1.

Investigation of shallower contours and greater ratios or contours of a modified design is

suggested.
Chrome carbide was confirmed as an excellent die material.
IV. Seventh Campaign at Dow
A. Purpose
The various purposes of this campaign were as follows:

1. Investigate the effect on yield of various billet back end contours, using both contoured

billets and contoured follower blocks.

2. Investigate the effect of two amounts of billet diametral upset on yield, and particularly
on rod surface quality.

3. Investigate the flow characteristics of uranium in the gamma phase by partially extruding
two billets.

4. Attempt to pierce a five-inch-long billet with a 6**

och-diameter graphite piercing
cap, a 6%-inch mandrel and a seven-inch die opening. This was intended to be a
preliminary investigation of a possible method for freeing rods from their butts.



Mr.
Mr.
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. Stevenson
. Teter

. Thayer

. Weber

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Technical Library
Technical Editor

CONEDSPrAL

Internal Distribution (continued)

No. of Copies

1

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V-40

B. Experimental Work

1. General

Procedures were essentially the same as those employed in previous extrusions at

Adrian, with the exception of those described below. Constant and variable extrusion

conditions are listed in Tables I and II, respectively.

Constant Extrusion Conditions-Ninth Gamma Extrusion Campaign

at BBC, Adrian, Mich.

Billet Temperature

Follower Block Temperature

Tool Oven and Container Temperature

Follower Block Material

Die Material

Die Design

Billet Diameter
Billet Length
Container Liner ID

Reduction Ratio

1900°F
1900°F
790°F
CS 312 Graphite

All. Lud. Grade CA815
Chrome Carbide Insert
(in A.LS.L H-21 Case,
Rg 46-50)

Shear Type, 3.475-in. ID,
*Ayin. entrant radius,
Yin. land, 5° relief
angle, no offset relief

6*54, in.
1054, to 16% in.
7.488 in.

4.6to1


IlI-19

For the first series of calculations, the results of which appear in Table I, it was desired to
determine the degree of conversion occurring in a one- or cwo-stage cylindrical fluid bed. Perfect
mixing was assumed, permitting the use of turaover-time distribution curves appearing in the
literature.* The reaction rate curve used for these and subsequent calculations was obtained by

the thermobalance technique.’ It is presented in Figure 1.

Table I

Reduction of Fluid-Bed-Denitrated UO, in Mulci-stage
Cylindrical Fluid-Bed Reactors

Case I-A Case I-B
Number of Stages 1 2
Feed Rate, Ib UO,/hr 80 80
Total Turnover Time, hr 3 3
Volume/Stage, cu ft” 1.2 0.6
Reaction Temperature, °F 1050 1050
Average Total Conversion, % 73 84

? Assuming 20% bed expansion and a bulk density of 237 Ib/cu fe.

Tt can be seen chat more than two stages would be needed for complete conversion of 80 Ib

UQ,/br, which is the anticipated production rate of the fluid-bed denitrator. In fact, ANL has

found that for an average total turnover time of 2.6 hours four stages were necessary to produce

98% UO,.° Of course, conversion could be increased by . making each stage larger or by considerably
reducing the feed rate, but for pilot plant. purposes, neither alternative is desirable.

“ Perey, John H. (Editor), Chemical Engineers’ Handbook, McGraw-Hill Book Company, Inc., New York (1950),
Ed. 3, p 1230-1231

© Ludwig, F. J., Mallinckrodt Chemical Works, Personal Communication

* Jonke, A. A., Chemical Engineeving Division Summary Report, October, November, and December, 1957, Argonne

National Laboratory, ANL-5820 (Febraary, 1958), p 49-52



II-14

As can be seen in the tabulated data, there is very little difference between the measurements
obtained with the continuous monitor and the bench meter. The maximum deviation obtained
was 0:4 pH units. Statistical analysis of the data indicates that no real difference can be

proven to exist between the two sets of data.

Conclusions

d Suggestions

The pH of refinery raffinate can be monitored with a continuous measuring system, providing

precautions are taken to prevent damage to the electrodes.

A suggested plant application of the continuous pH monitoring system is shown schematically
in Figure 2. The control system is arranged so that the raffinate is continuously recycled
through the neutralization cank during the addition of lime. After neutralization, the lime
addition would be stopped and the raffinate pumped to the storage ponds automatically by

closing the valve in the recycle line and opening the valve in the pump-out line.

Arrangements should be made to flush the measuring chamber and check the zero drift of che

inscrument periodically.



Report Number: MCW-1416 Subject Category: Technology - Feed Materials
Date of Issue: August 1, 1958 Title: PROCESS DEVELOPMENT QUARTERLY
REPORT, PART If - PILOT PLANT WORK

External Distribution

No. of Copies
Aeroprojects, Inc. 1
Air Technical Intelligence Center
Allied Chemical and Dye Corporation
Argonne National Laboratory
Armed Forces Special Weapons Project, Sandia
Armed Forces Special Weapons Project, Washington
Atomic Energy Commission, Washington
Babcock and Wilcox Company (SOO-274)
Battelle Memorial Institute
Bridgeport Brass Company
Chicago Operations Office
Chicago Patent Group
Division of International Affairs (Pennington)
Division of Raw Materials, Washington
duPont Company, Aiken
De. M. H. Wahl
Me. T. C. Evans
Dr. R. T. Huntoon
Fernald Area Office, Mr. C. L. Kart
General Electric Company, Richland
Dr. S. H. Bush
Dr. J. J. Cadwell

Mr. S. M. Gill

Mr. R. E. Olsen (3703 Building)
Dr. P. H. Reinker

Mr. K. V. Stave

Mr. F. W. Woodfield

Dr. L. P. Bupp and Dr. J. F. Music

Mr. J... Stringer

Goodyear Atomic Corporation

i or oe Cee a on aro ar oar a ore rome



V-69

Billets having contours machined on one end were used in all cases. Billet 9 was

machined as shown in Figure 9 to simulate the shape expected of Weldon Spring dingots.
Billet Heating

During heating of the first billet in the coil which had been damaged during the seventh
campaign and subsequently repaired, the liner gap closed. The billet was partially
melted in the vicinity of the gap, but extruded. The damage to the liner precluded
further use of this coil and the balance of the billets for the campaign were all heated

in the other coil.

The Rayotubes and recorders had been erroneously calibrated on a black body and
therefore did not indicate true temperature on the first billets. Since the only reliable
calibration method has been found to be calibration of the instruments at the phase
transformation temperatures, it was necessary to heat several billets before reliable

temperature readings were obtained

Heating of the capered billet, No.9, proceeded without incident. However, the

temperature was estimated to be about 50°F lower at the small end than at the large end.

Extrusion

An articulated dummy block, bored and threaded to receive a mandrel, was used for all
extrusions in this campaign. This was the same dummy block as the one used with a
piercing mandrel attached to it in the eighth campaign for punching, but in the ninth
campaign it was attached to the ram. A blank to protect the threaded hole shown in
Figure 10, was inserted before each extrusion. Only two turns of the threads were
required to insert or remove this blank. Various combinations of the follower blocks
shown in Figure 11 were used in conjunction with this blank for extrusion. The

arrangement of follower blocks for the various billets is shown in Figure 12

After extrusion of Billets 1-6 and 9, the ram was retracted and the blank was removed
from the dummy block. The bushing shown in Figure 13 was then inserted, also by

only cwo turns of the threads, and a punch of the design shown in Figure 14 was
inserted in the bushing. Punches having three front face diameters were used, as shown
in Table X. The ram was advanced until the frone of the punch was beyond the face of
the die for Billets 1 and 2, but was stopped when the front of the punch was juse short
of the die face on Billets 3-6 and 9. The latter procedure required the graphite behind
the billet to perform the shearing action through the die required to free the rod from its
butt. Damage to the bushing during punching of the first two butts caused misalignment

of the punch which resulted in breakage of the three punches and damage to the die.



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VI-91

FIGURE 5

PRODUCT FILTER BAG PRESSURE DROP VERSUS CUMULATIVE PRODUCTION

4.0 9

3.5

2.0

15 KF

Pressure Drop Across Product Filter Bag, inches H20

° n ! !
0 500 1000 1500 2000

Pounds Micronized UO2 Through Product Collector



I-11

CONTINUOUS pH MEASUREMENT OF NEUTRALIZED RAFFINATES

by

N. G. Holloway

Summary

A continuous pH monitor operated satisfactorily in neutralized raffinate slurry for a period of one

month in the pilot plant. No evidence of electrode deterioration could be detected.
Introduction

Before the refinery raffinace is pumped co the disposal pits, it is neutralized with lime to minimize
acid pollution of the countryside and to protect the quarter mile of carbon steel transfer line. At
present the raffinate neutralization operation is controlled by means of samples analyzed in the
laboratory. An instrument chat would continuously monitor raffinate pH would (1) simplify refinery
operations, (2) provide an automatic safeguard against inadvertent pumping of acid raffinate to the
pics, and (3) minimize present excessive overneutralization of raffinate, with resultant lime cost

savings.
This report describes pilot plant tests of a continuous pH monitor on neutralized plant raffinates.

Description of Materials and Equipment

A schematic flow diagram of the cest stand is shown in Figure 1. Neutralized plant raffinace was
pumped out of a hold cank through a cell containing the rest electrodes and back again into the
hold tank. The electrodes used in this test were standard Beckman electrodes; the glass
electrode was Mode! No. 4990-80 and the reference electrode was Model No. 4970. For plant use

a larger reference electrode, such as the Beckman No. 8970-90, is recommended with a No. 4990-83
glass electrode. The meter used in this test was a Beckman Model N; however, in plant use a
heavy-duty industrial type like the Beckman Model W meter would be used in conjunction with any
standard recorder-controller

The vessel in which the electrodes were mounted was designed to minimize the problems of
handling a slurry. In order to prevent build up of solids in the chamber the bottom was sloped and
the effluent discharged from the bottom at the lowest point. Raffinate was introduced into the
chamber through the top at a point opposite to the discharge. The vessel was vented, and the
discharge opening was slightly smaller chan the inlet. The electrodes were mounted through the
top of the chamber. By using this type of vessel che flow could be regulated to keep the chamber
full under atmospheric pressure and to prevent scale formation on the electrodes.



VII-97

Figure 2

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VII-99

The heaviest boule of pure UO, grown to date is Boule 22. Boule 21 is the longest yet produced.
Boule 18 was produced at the highest growth rate yet achieved. Boule 15 has the highest

density yet achieved

The largest pure UO, boule reported previously was Boule 7,? which weighed only 26 grams. It
was one-half inch in diameter by five-eighths inch long and was produced at a cate of 26 grams of
UO, per hour. The density of Boule 7, the highest previously reported for pure UO,, was only

86.0% of the theoretical maximum.

The density of the boules is measured by weighing them in air and then immersed in mercury. The
previous low densities obtained appeared to be caused by occlusion of gas in the boules during
the melting operation. Examination of the more recent boules which have higher densities indicates

that much less gas was entrapped.

The improvements in size, growth rare, and density of the boules grown are due both to faster probe
rotation and mechanical improvements in the apparatus such as the addition of the fusion chamber
and to better electrode positioning control. Boules up through number 14 were grown with a probe
rotation speed of 1.5 rpm. Boules 15 through 23 were grown with probe rotation speeds of 110 rpm
or more. Fast rotation helps prevent the formation of large piles of powder on top of the boule
under which gas can be trapped. The use of very fast feed rates, however, such as were used in

producing Boule 18, can still deposit piles of material which trap gas and cause lowered density.

Several boules have been polished and etched to determine the grain size. The specimens were

1) imbedded in thermoplastic, 2) polished with 180-grit silicon carbide, and 3) further polished
with diamond dust. Then the sample was etched with 10 v/o concentrated H,SO, ~ 90 v/o hydrogen
peroxide (30% solution) for approximately one minute. Microscopic examination showed that grain
sizes up co one-eighth inch in diameter have been attained. Figure 4 shows the top of Boule 19
prior t’ polishing and etching. Some of the grains in this surface of last solidification are as

large as one-sixteenth inch in diameter.

The polycrystallinity of the boules is evidently due co the manner in which the UO, is solidified
rather than co any influence of the polycrystalline nature of the seeds. Slivers were taken from
Boule 19 and used as seeds for growing Boules 20 and 21. Figure 5 shows these silvers of UO,
prior to their removal from the boule. The cross-sections of each Sliverwere monocrystalline, but
Boules 20 and 21, which were grown from them, were polycrystalline. Reducing the thermal

gradients in the top of the boule as it is being grown may allow the growth of larger crystals.

? Hedley, W. H., Process Development Quarterly Report, Part II, Mallinckrodt Chemical Works, MCW-1406
(Auguse 1, 1957), p 57-59



M-21

Calculations for a tapered-shell fluid-bed reductidn reactor are presented in Table Il. Again the
basis was a production rate of 80 Ib UO,/hr. A particle size range of -35¢o +65 mesh was used,
for which 237 Ib/cu ft and 1.5 to 1.8 ft/sec are reasonable values of the fluidized density and

fluidizacion velocity range, respectively. ’ For these computations 1.8 ft/sec was assumed as

the fluidizing velocity. Reaction temperature was set at 1050°F.

Toral average turnover time

was set at 2.5 hours. This value is higher chan the 120 miautes needed for complece conversion

because the tapered bed does not exhibie perfect “piston” flow; this value is also consistent

with the Argonne daca mentioned above.

Table Il

Reduction of Fluid-Bed-Denitrared UO, in a Tapered Fluid-Bed Reactor

Bases for Calculated Data:
Feed Rate
Feed Particle Size

Superficial Fluidizing Velocity at

80 Ib UO,/hr
35 co +65 mesh

Bed Conditions 1.8 ft/sec

Fluidized Density 237 Ib/cu ft

Reaction Temperature 1050°F

Turnover Time 2.5 he

Case I-A Case II-B Case II-€ Case II-D

Fluidizing Gas Flow, SCFH 300 400 500 700
Bottom Cone Diameter, in. 3.6 4.5 5.2 6.6
Top Cone Diameter, in. 5.0 5.7 6.4 7.6
Height of Bed, fc 8.4 6.0 4.6 3.1
AP Across Bed, psi 13.8 9.8 7.6 5.1

7

~) 1017-P (June 18, 1958)

Robinson, S. N., and Smith, W. J. S., Report on Tripto Y-12, Mallinckrodt Chemical Works, Project Memorandum



Billet Heating

When the power was turned onin the “B” coil, during the course of checking the
control circuits prior to the start of the campaign, a short circuit between turns
damaged the coil and precluded its use in this campaiga.

Both coils had been modified before this campaign to improve their alignment in an
effort co prevent short circuiting of the gap in the stainless steel liner. Also, a

layer of Fiberfrax, a fibrous paper type insulation, was glued with waterglass to the
inside of each liner to prevent contact of the billet with the liner. A piece of graphite
16 inches in diameter by 18 inches long was heated to 1750°F in the “A” coil to dry

out the Fiberfrax before heating a billet.

During heating of the first billet, part of the Fiberfrax in the “A” coil slid down and
obstructed the view of the Rayotube. There was therefore no temperature control
during the latter part of the heating of this billet and it was partially melted. The
billet was placed in a steel box and covered with salt after removal from the coil,
and the Fiberfrax was then completely removed from the coil liner. A small portion
of the second billet heated was melted adjacent to the liner gap near the bottom, but

the billet was extruded.

Ab attempt was made to use firebrick discs as stools to support the billets in the coils,
in order to decrease heat loss from the billet and to prevent overheating of the bottom
flux concentrator. These discs did not have sufficient strength to support the billets
during lifting in che grab and their use was abandoned after the fourth billet.

The uranium follower blocks for use in the partial extrusions were placed on top of the

billets in the coils and heated with the billets.
Extrusion

Handling of the hot graphite follower blocks, heated to 1850°F in an electric resistance

furnace, again presented operational difficulties and resulted in long transfer times.

Two 16%-inch-diameter and three 15 4-inch-diameter billets were extruded with
contoured graphite follower blocks to determine the effect of degree of upset in the

17-inch-ID container linec.

The two billets partially extruded for study of flow characteristics were 15% inches in
diameter so that che maximum effect of upset in the 17-inch-ID liner would be observed.
When the first of these had been inserted in the container, the ram was advanced until



VII-95

Figure 2 shows a general view of the flame fusion equipment. The flanged gas-tight chamber at
the top of the unit houses a Syntron vibratory feeder. Variation of the vibration speed permits
control of the cate at which the feeder discharges powder. The tube from the bottom of the

chamber discharges the powder and entraining gas directly above the seed rod.

The positioning of the seed on its supporting probe in a fixed horizontal plane at the hottest
zone of the arc, is achieved by continuously lowering the probe at a rate coninciding with the
rate of crystal growth in the flame. The platform on which the probe is mounted is controlled by
twin screws which are driven by a variable speed motor. The lowering rate may be set anywhere
within che range of 0.001 to 1.25 inches per minute. Lateral adjustments of the probe and fusion
chamber are also available to assist in obtaining the proper coordination of the feed, the seed,
and the probe. The probe rotation speeds which have been used vary from 90 revolutions per

hour up to several hundred revolutions per minute.

As the fused tod is lowered, it enters a cooling chamber which protects the UO, from oxidation
while it is being cooled. Inert or reducing gases flowing upward through the chamber serve as
both protective and cooling media. The actual melting takes place within a refractory lined
fusion chamber which is equipped with an off-gas removal vent. This minimizes operational

hazards such as exposure to heat, ultraviolet light, and uranium oxide fumes.

Experimental Results and Discussion

A summary is given in Table I of the weight, length, diameter, growth rate, and density of UO,

boules grown since the last report. Figure 3 showsa photograph of Boules 16 and 18.



IV-33

Table IV

Uranium Content of Fluorinated MFL versus Slag Feed Rate and F, Excess

Slag Feed Rate Toral U u Unoxidized U
lb/hr F, (x theory) % % %
15 9.25 0.15 - -
25 5.55 0.20 0.014 0.16
40 3.47 0.19 <0.005 0.14
50 2.78 0.16 <0.005 <O.1 .
100 1.39 0.14 <0.01 0.1

* The term “unoxidized U” as used here denotes uranium with a valency of +4 or less.

Table V

Uranium Content of Fluorinated MFL versus Sieve Fraction

Total U u° Unoxidized U
Sieve Fraction % % %
Run 4
+100 Mesh 0.21 <0.01 0.13
-100 to +200 0.21 0.01 0.20
-200 to +325 0.20 0.02 0.19
7-325 0.21 0.02 0.22
Run 5
+100 Mesh 1.0 0.1 0.94
~100 to +200 1.4 0.1 1.0
~200 to +325 1.8 0.04 13
325 43 <0.01 0.96

@The term “unoxidized U* as used here denotes uranium with
a valency of +4 or less.



I-17

PRELIMINARY DESIGN OF A PILOT-PLANT
UO,-REDUCTION FLUID-BED REACTOR

by

S. N. Robinson
W. J. S. Smith

B. E. Zimmerman

Summary

Calculations have been made for the design of a fluid-bed reactor for the continuous reduction of
fluid-bed-denitrated UO, to UO, with cracked ammonia. A bed of varying cross-section was chosen
to permit approach to “piston” flow of solids. A bed with cylindrical sides containing a tapered
mandre) was selected in preference to a bed with tapered sides because of ease of fabrication and

greater flexibility.

For a processing rate of 50 Ib UO,/hr with UO, in the minus-35 to plus-65 mesh particle size range,
a reactor shell 5 inches in diameter and 4.4 ft tall was indicated. A tapered mandrel, 2.89 inches

in diameter at the bottom and 0.63 inches in diameter at the top, is required.
Intcoduction

Currently there is a strong impetus for investigation of fluidized-bed techniques for the various
gas-solids processes encountered in the uranium feed materials industry. Chief reasons for this
impetus are that fluid bedsare free of moving parts, are simple to construct and maintain, are
virtually isochermal because of high vertical and horizontal heat transfer coefficients, permit easy
handling of the solids, and provide the best possible gas-solids mass transfer. However,
conventional fiuidized beds are also aimost perfect mixers. This fact, of course, means that for
fluid beds used as reactors some of the solid particles are in the bed an insufficient time for

complete reaction. To insure complete conversion, rhen, it becomes necessary to

1) build che reactor large enough to provide a iong turnover time, which then assures that,

say, 98% of the solids are present the required time for complete reaction, or,

2) cascade several reactors either vertically, so that the same gas fluidizes each stage, or

horizontally, with parallel gas flow.

Most uranium compounds have high bulk densities and consequently require high fluidizing gas
tates. Because of this fact it is usually impsactical co build long curnover-time reactors.
Horizontal multi-stage reaccors exhibit the same large gas consumption (heretofore the exiting gas

from one stage has not been used to fluidize another stage). Vertical stages offer economical gas



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CONSADENTTAT.

External Distribution (continued)

Hanford Operations Office
Iowa State College
Mound Laboratory
National Lead Company, Inc. (Winchester)
National Lead Company of Ohio
Dr. D. S. Arnold
Mc. C. E. Polson
Dr. C. E. Crompton
New Brunswick Area Office
New York Operations Office
Nuclear Metals, Inc.
Oak Ridge Operations Office
Parent Branch, Washington
Power Reactor Development Company
Union Carbide Nuclear Company (ORGDP)
Union Carbide Nuclear Company (ORNL)
Union Carbide Nuclear Company (Paducah Plant)
Vitro Engineering Division
Technical Information Service Extension, Oak Ridge

No. of Copies

1

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VII-93

FLAME FUSION STUDIES

by
W. H. Hediey
R. J. Roehes

Summary

The flame fusion technique has been used to grow specimens of UO, up to 3% inches long,
weighing up to 83.5 grams. containing crystals up to one-eighth inch in diameter and having
densities up to 98.1% of the theoretical maximum. Pure UO, powder has also been converted

into high purity UO, boules by this technique.
Introduction

The purpose of this project is to produce monocrystalline pieces of UO, having the maximum
density theoretically possible (10.97 grams per cc). The flame fusion or Verneuil method’ has
been used in attempts to achieve this aim. It consists of progressively melting uranium oxide
powder and solidifying it to form solid shapes known as boules.

Equipment and General Procedure

In recent work on this project an atomic hydrogen arc has been employed to attain the temperature
necessary to melt UO,. Figure 1A shows a seed rod supported on a rotating, water-cooled probe
which positions it during the growth operation. The seed may be a pressed and sintered compact
or a single crystal from a previous run. Approximacely one-half of the cop of the seed is kept
molten (Figure 1B) by the hydrogen arc while fresh powder awaiting fusion is being deposited on
the other half. Feed powder such as UO, or UO, is carried through a tube by entraining gases
which exit above the seed directly opposite the hottest zone of the arc. As the probe is rotated,
the feed powder continues co deposit on the top of the seed and then move into position directly
under the arc where melting takes place (Figure 1C). The rotation of the probe spreads the
powder evenly over the top of the seed. The surface tension of the molten liquid with the sharp
thermal gradient between the molten top and the solidified edge below it tends to prevent the
liquid from flowing down the sides of the seed rod. The probe is gradually lowered so that the
top of the growing UO, rod remains in a fixed horizontal plane that is favorable for an equilibrium
of heat transfer. Figures 1D and 1E show the formation of a UO, boule by progressive melting
and solidification. The seed is protected at all times from the atmosphere by a reducing gas

envelope.

* Verneuil, A., “Growing Synthetic Rubies by Fusion,” Compt, Rend. 135, 791-794 (1902)



V-38

C. Eighth Campaign at Dow

1. Separation of rods from their butts by partial extrusion of copper, cast iron, and uranium
follower blocks was not successful. The temperatures at which the copper and cast
iron follower blocks were used were not high enough to impart sufficient malleability
for extrusion, while the uranium follower block adhered firmly to the back end of the

rod after extrusion.

2. A rod was separated from its butt by “punching,” using a 2:6-inch-diameter mandrel

without a piercing cap, and a seven-inch-ID die. A 1400-ton thrust was used in punching.

3. Two rods were separated from their butts by “punching” with a 6%-inch-diameter mandrel
without piercing caps, and a seven-inch-ID die. Respective thrusts of 1400 and 400 tons

were used in the punching operation.

4. A billet composed of one-inch-thick slices welded together was extruded for a study of

the flow pattern of gamma uranium by radiographic examination.
5. The chrome carbide insect die used was again damaged by the action of the shear.
D. Ninth Campaign at Dow

1. Six rods were separated from their butts by “punching,” using punches of three diamecers
and both plugged and solid follower blocks. It was not necessary to move the punch
through the die to effect the separation when sufficient follower block graphite

preceded the punch.

2. Follower blocks weakened by having annular grooves machined in their back face were

not effective in separating rods from their butts.

3. A tapered billet, approximating the shape expected in the Weldon Spring operation, was

heated and extruded without incident.

4. Two flow-type chrome carbide insert dies were damaged during the punching operations

because of punch misalignment, but produced rods of ‘satisfactory surface quality.
IL. Introduction

Gamma extrusion has been chosen as the primary forming operation to be used at the Weldon

Spring plant in the preparation of dingots for rolling at NLO.' Installation of the 1750-ton press

* Becker, R. W., Hansen, J. W., Schaffer, H. J., Hartmann, R. F., Process Development Quarterly Report, Part If,
Mallinckrodt Chemical Works, MCW-1402 (May 1, 1957), p 133-150 @



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1/2 tn. °
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A
5 nal
Dimension, in.
A} 5

2-1/2] 4-1/2
3 5

3-12] 5-1/2

FIGURE 1

CONTOURED GRAPHITE FOLLOWER BLOCK